Cellulose nitrate multiacylate compounds and process of making the same



exce tche number or the fatty acid radicals of AS ill, be ema led fir 45 Exampleq corresponding to the fatty acids of 2-6 carbon 45 Patented Feb. l2. 1935 I a u r 1 99 ,1 5 a d '1,991,12 5, I CELLULOSE 'NITRATE M'ULTIAGYLA'DE COM- POUNDS AND PROEESS THE AM C r l u nd J m T- Rpchest c N. Y.,' assignors; to Eastman- Kodak- Company; Rochester, N. Y., a corporation of NewYoik N Drawing. Applicationlneccmliclal 193%,

UNITED srArEs PATEN'l s rial .No. 505.95,; y l 13 Claims. (01. zen-m V Thisinvention relates to a process of. preparing time .6135- minutes p tererredl it is subjected mixed cellulose esters containing one. nitro and to a; temperature QfixfiQ-GQ Cw I he dope formed;

at least two acyl groups oixthe low-er aliphatic may be precipitated: in cold alcohol desired acids which, are produced by pro-treating the Cellujlq c. mtr cmec nte-hutyrate will be found cellulose wlthone of theacidsand subse uently to result from mistreatment. y .5

treating it with the anhydride or, 'anhydrides of x m H the remaining fattyacid or acidsaandl a liquid. '1 a oxide of nitrogen. It is preferred that a catalyst .Tc about 5, gr ms, o cel ulose s add d, a miss preferably a sulfuric: phosphoric acid mixture be i ture of fife-6Q; grams; of; alerie. acid and a small 1o used in thisprocess. v amount" oi? a mixed catal st, The material is 1o Our invention has for its object the production heldat a-temperatureof 5Qv-6 Q G. iorabout -20 of esters of cellulose containing anitrate and hours-pill? 151 21 8 1 Q99 t9. 31 .0 1? 29: 5 Cc two ormore fatty acid radicals: of 2 to 6. carbon 3%351; swarms, nh d idc-a e. added? atoms each. These compounds combine all the mixture well as-itat t end iiu l-alll Q? is. advantages oft-he various individual radicals such liquid; Nearsadded withac nti ous as flexibility, non-infiammab-ility, and transpare The material. is, t r main t a t mp ra: ency, and the disadvantages, if any, of each radl-i ture of fill-:? il a mccsi ,EX 1.3 11 1 cal combinedwith the cellulose is either reduced is then subjected to a temperature of 59:69 C to. a minimum or completely obliterated, The dcneamax beprccipitated a oho sin the 2 we have found that mixed esters of cellulose previous. examplm. Cellu ose. ni ra e-3.1 813% 2.

of varied properties may be produced by-combinzcaproate will be found to result from this treating the fatty acid radicals having from. 2to 6 mente i i. carbon atoms with cellulose,;together with the I Example 111 nitrate group. .Thewfatty acidradicals which may be substituted include the normal radicals and also the radicals isomeric to thenormal radicals. Where the terms butyric, Valerie; or canv p 1) 05124532; rgggtalgfigi proic or terms corresponding to theseare used s" f 1" rc eh u s sp c fic ti n it i intended t at tum-mm m 15-20 hours t agree (if cl ljc c is P ace d t ll it 25 t I Al'mixture of ut 20. cc. cryaiericanhydride 0,-. both the normal and the isomeric radicals are. mi A i 39, cludedin this terminology. Y and about .10 Q ut rwenhydndc is then Although in the examples giyen less than five a gi W fi fi ii i gg gf t g substituent radicals are introduced into the "'9 i f 9: w cellulose, a compound havingmore than four Y P d itt9 ta short radicals has not been found of sufficient utility mz s iprgiligmi a i tllhgn b .5. to be concerned about at the present time. How- W 'e a whet" 519m ever, Within reason, thereiis no limit to the numm then be pf t lfi f fi i ll d her of fatty acid radicals that may be substituted mi hl e re alert??? i 9 with the nitrate group in the-cellulose molecule firom twat-m? l a a he exam le he 10 2-6 carbon atoms. l ntccessccmp ises re t ne ce lull sey hgn 9 The following examples are given as illustrafatty e Of carbon atoms and an tions of Specific embodiments of our invention ation catalyst (which catalysts are well known in the art), then adding one or more acid anhydrides To about 5 grams of cellulose (cotton. lintersl atoms P hquid higher oxlfle of f The is added a mixture f about grams of glacial fatty acids or anhydrldes suitable in this process acetic acid and a Small amount of mixed t are acetic, propionic, butyric, valeric and caproic. t 1 t 95% 30 3 parts f 95% If it is desired to substitute unsaturated acyl o0 This mixture isauowed to Stand f r 15 20 hours groups the anhydrides or acids of the oleic series at about 20-25" C. after which 20-25 grams of of c o at uc a ac yl c cr cn c, butyric anhydride are added and the whole is angelic d x i a ds r t is meric acids thoroughly mixed. There is then added with thereof'may be substituted for the saturated acid stirring l 0.0. of liquid N02. After the material or acid anhydride in this process where desired. is held at a temperature of 20-2 5 C. for a short If desired a halogen may be added after acyla- 5 which they are added may be varied to satisfy the requirements of the finished product. In general, the acyl 'groups.containing the fewer number of carbon atoms are the more readily introduced. v

It is to be understood that other acylati on catalysts and oxides of nitrogen having a comparatively high boiling point such as N203 and N205, other than those given in the examples. may be used in this process. Obviously, N02 and N204 are used synonymously in the examples.

' Some of the compounds which we have found may be prepared by this process are the following: Cellulose nitro-aceto-propionate,- cellulose nitro-aceto-butyrate, cellulose nitro-aceto-valerate, cellulose nitro-aceto-caproate, cellulose nitro-propiono-butyrate, cellulose nitro-propionovalerate, cellulose nitro-propiono-caproate, cellulose nitro-butyro-valerate, cellulose nitrobutyro-caproate, cellulose nitro-valero-caproate. f the cellulose esters with four acyl groups the following are'among those which may be prepared by this process: Cellulose 'nitro-acetobutyro-valerate. cellulose nitro-aceto-propionocaproate, cellulose nitro-aceto-propiono-valerate, cellulose nitro-aceto-butyro-caproate, cellulose nitro-aceto-valero-caproate, cellulose nitro-pro piono-butyro-valerate, cellulose nitro-propionovalero-caproate, cellulose nitro-propiono-butyrocaproate.

What wenow claim as our invention and desire to be secured by Letters Patent of the United States is: 1 Y

1. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with a lower aliphatic acid, and treating the re- 7 sulting productwith a knownliquid oxide of nitrogen having a boiling point of approximately 3.5 C. or more and at least one lower aliphatic acid anhydride of another aliphatic acid.

2. A process of making a cellulose "nitrate multi-acylate which comprises treating cellulose with an aliphatic acid of 2-6 carbon atoms and thereafter treating it with'a known liquid oxide of nitrogenhaving a boiling point ofapproximately 3.5 C. or more and at least one aliphatic acid anhydride corresponding to an acid of 2-6 carbon atoms other than that with which the cellulose was treated initially..

3. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with an aliphatic acid of 2-6 carbon atoms and thereafter treating it with at least one aliphatic anhydride corresponding to an acid of 2-6 carbon atoms other than that with which the cellulose was treated initially and a liquid oxide of nitrogen selected from the group consisting of N02, N204, N203 and N205. 4

4. A process. of making a cellulose nitrate multi-acylate which comprises treating cellulose with an aliphatic acid of 2-6 carbon atoms and thereafter treating it with a known liquid oxide of nitrogen having a boiling point of approximately 3.5 C. or more and an aliphatic acid anhydride corresponding to an acid of 2-6 carbon atoms other than that with which the cellulose, was treated initially.

5. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with an aliphatic acid of 2-6 carbon atoms and thereafter treating it with a known liquid oxide of nitrogen having a boiling point of approximately 3.5 C. or more and a plurality of aliphatic acid anhydrides each corresponding to anacid of 2-6 carbon atoms other than that with which the cellulose wast'reated initially.

6. A process of making cellulose nitrate multiacylate which comprises treating cellulose with glacialacetic acid and thereafter treating it with a-known liquid oxide of nitrogen having a boiling point of approximately 3.5 C. or more and at least one aliphatic acid anhydride corresponding to an acid of 2-6 carbon atoms other than that with which the cellulose was treated initially.

7. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with glacial acetic acid and thereafter treating it with liquid N02 and at least one aliphatic acid anhydride corresponding to an acid of 2-6 carbon atoms.

8. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with glacial acetic acid and thereafter treating it with liquid N02 and butyric anhydride.

9. A process of making a cellulose nitrate multi-acylate which comprises treating cellulose with glacial acetic acid and thereafter treating it with liquid N02 and valeric anhydride.

10. A' process of making a cellulose nitrate multi-acylate which comprises treating cellulose with glacial acetic acid and thereafter treating it with liquid N02 and butyric and valeric anhydrides.

11. A cellulose derivative which contains a nitrate group and three different aliphatic acyl groups each containing 2-6 carbon atoms.

. 12. Cellulose nitrate acetate-butyrate-valerate.

13. Cellulose nitrate-acetate with a plurality of acyl groups of 2-6 carbon atoms other than acetyl attached thereto. 7 I

CYRIL J. STAUD. JAMES T. FUESS. 

